Anthraquinone dyestuffs and process for their production



United States Patent 6 Claims. (51. 260-243) It has been found that valuable anthraq-uin-one dyestufis are obtained by reacting an-thraquinone derivatives carrying a hydroxy group or an amino group in the 1-position and in the 4-, and/or 8-posi'tion, an hydroxy, amino or nitro group with aromatic amines of the general formula In this formula, Y denotes the residual constituent of a nitrogen-containing 5- or 6-membered ring, for example an alkylene chain, which may be interrupted by carbonyl groups and/or hetero atoms such as oxygen, nitrogen, sulphur or sulphur dioxide.

The dyestuffs obtain-ed may be characterized by the following formula 3 R2 wherein R R R and R represent a radical of the formula wherein Y denotes the residual constituent of a nitrogen containing 5- or 6-membered ring, whereby said radical is contained once or twice in the anthraqu-inone mole cule, R represents furthermore to a member selected from the group consisting of a hydroxy and an amino group, R and R represents furthermore a member selected trom t-he groups consisting of H, N0 NH and OH and their chlorine and bromine derivatives. Examples of the aromatic amines to be used according to the invention are the sul-tames of 4- (rnor p-aminophenyl amino) butane -sulphonic acid, the N-(mor p-aminophenyl)-succinimide, -glutarirn-ide or -diglycolic acid imide, N-(mor p-aminophenyD-py-rrolidone, l-(paminophenyl) -1,2,4-triazole and N-(por :o-aminophenyl)-morpholine or -thiomorpholine which may carry ,further substituents such as halogen or alkyl preferably lower .alkyl or other non-.watensolubilizing groups.

For the reaction there may be used anthraquinones which may carry further substituents in the 5- and 8 position, e.g., halogen atoms, hydroxyl, nitro or posisib-ly substituted amino groups. Examples of such compounds are 1-hydroxy-4-nitro-anthraquinone, l-methoxy- 4-nitro, -4-chloro, or bromoenthraquinone, .1,5-dihy d-roXy-4,8-dinitroand 1,S-dihydroXy-4,5dinitro-anthraquinone or mixtures thereof as well as leuco-dA-dihydroxy-anthraquinone or mixtures of the latter with 1,4- dihy-droxy-anthraquinone or leuco-l,4,5,8 tetra-hydroxyanthraquinone.

The reaction of the anthraquinones with the aromatic amines of the general Formula I can be carried out by 3,184,455 Patented May 18, 1965 methods usually applied in anthraquinone chemistry tor react-ions of this type, for example by reacting hydroxya-nthraquinones in admixture with their leuco-compounds or nitroanthraquinoncs with suitable aromatic amines. The process is preferably carried out in a temperature range between 40 C. and 200 C. and in inert solvents such as alcohols, glycolmonoalkyl ethers, pyridine, nitrobenzene or dimethylformarnide.

When leucofianthraquinones are used for the react-ion, the leuco-anthraquinones are subsequently freed from their leuco hyd-rogen oxidatively in conventional manner.

If the dyestutfs obtained by the process according to the invention still contain n-itro groups, the latter can be reduced to amino groups by means of :known reducing reaction-s. Furthermore, the dyestuffs obtained can be after-halogenated in conventional manner, for example with bromine or sulphuryl chloride in sulphuric acid or organic solvents so that the halogenated dyestuffs preferably contain 0.5-2 halogen atoms :per dyestutf molecule.

The new dyestuffs produced according to the invention are preferably suitable for the dyeing of hydrophobic materials such as fibres of cellulose acetate, polyamides and, in particular, aromatic polyesters. Dyeings in red to blue shades are chiefly obtained. Some blue dyestuffs are distinguished by a highly desirable greenish shade which is not obtainable with the known dyestuifs of similar structure. The dyestufis further possess very good tastness properties, especially a very good fastness to light, washing and sublimation.

The ttollowing examples are given for the purpose of illustrating the invention; the parts are par-ts by weight, unless stated otherwise.

Example I (a) \150 parts of 1,5-dihydroxy-4,-8-dinitro-anthraquinone and 188 parts of N-(p-aminophenyl)-pyrrolidone in 1500 parts of glycol monoethyl ether are heated to the boil, until the starting material can no longer be detected by paper chromatography. After cooling, the melt is poured into 7500 parts of 10% hydrochloric acid, the precipitated dyestuif filtered oif and washed with water. The dyestuif obtained which possesses the formula r t e to (l NH-O-Q is transformed into a finely dispersed form in known manner, for example by pasting with sulphuric acid, grinding the paste, after washing until neutral, with sulphite-cel-lulose Waste liquor and an alkylnaphthalenesulphonic acid and subsequent drying.

-A dyebath is prepared containing a dispersion of 1 part of the dyestulf described above and 20 parts of cresotic acid methyl ester in 4000 parts of water and adjusted with sulphuric acid to .a pH value of 4.5 parts of polyglycohterephthalate fibres are introduced into the dyebath at 50 C., the bath is heated to 100 C. within 2030 minutes and kept at this temperature for 1 hours. After rinsing and drying of the fibre, a very clear greenish blue dyeing is obtained which is distinguished by very good fastness to Washing and light and excellent tastness to heat.

It the dyeing process is carried out in the absence of cresotic acid methyl ester at C. for l1 /2 hours, a

very clear greenish blue dyeing is likewise obtained which has similar t-astness properties.

(12) In a similar manner, a greenish blue dyestuft is obtained from 1,5-dihydroxy-4,8-di-nitro-anthraquinone and N-(maarninophenyl) pyrrolidone. Instead of 1,5- dihydroxy-4,8-dinitro-anthraquinone there may also be used a mixture of 1,5-dihydroxy-4, 8edinitro- :and 1,8 dihydroxy-4,S-dinitro-anthraquinone as well as a mixture of N-(m-aminophenyD- and N-(p-am i-nophenyl)-pyrrolidone yielding dyestuffs with a very similar shade.

(c) 15 parts of the dyezstufi obtained according to Example 1(a) are dissolved in 185 parts of 100% sulphur-ic acid, stirred with 5 parts of ibor-ic acid and 0.1 part of iodine and treated with 5.2 parts of bromine. The mixture is stirred at 50 C., until .a processed dyestuif sample contains about 20-22% of bromine, poured into ice-water mixed with some 'bisulphite liquor, the precipitated dyestuif is filtered oil? with suction and dried. The dyestult, brought into a finely divided form, dyes polyester fibres in intense greenish blue shades. A similar dyestutt is obtained by introducing, instead of bromine, a corresponding amount of chlorine into the sulphuric acid solution.

(d) parts of the dyestuif obtained according to Example lt(a) are heated in 160 parts of o-d-ichlorobenzene with 0.1 part of iodine and 2.65 parts of bromine to 50 C., until a dyestuif sample contains about 9% of bromine. The 'o-dich-lorobenzene is driven off with steam and the dyestuif isolated in known manner. The dyestuif, brought int-o a finely divided tori-n, dyes polyester fibres in greenish blue shades and possesses a somewhat better aifiuity than the non-bromin-ated dyestuff. A dyestufl with similar properties is obtained by replacing the bromine by a corresponding amount of sulphuryl chloride.

(2) parts of the dyestuif obtained according to Example 1(a) and brought into a finely divided form by pasting with 80% sulphuric acid are heated in 800 parts of water with 7 parts of sodium hydroxide and 20. parts of glucose to 90 C. for about minutes, filtered off with suction, washed with water and dried. The dyestufi' thus obtained and having the formula H N O dyes polyester fibres in more reddish shades than the product obtained according to Example 1(a).

' (f) 10 parts of the dyestufi produced according to Example 1(a) are heated in 130 parts of o-dichl-oro benzene with 0. 1 part of iodine and 3.8 parts of bromine to 5 0 C., until an isolated dyestufif sample contains about 12% of bromine. The oichlorobenzene is driven off vwith steam and the dyestuif isolated in known manner. The dyestutt dyes polyester fibres in intense blue shades.

(g) A dyebath is prepared which consists of a dispersion of 1 part of the dyestuft described in Example 1(a) and 10 par-ts of a mixture of parafiin sulphonic acid sodium, oleyl-polyg'lycol ether and tatty acid-hydroxybenzylamidepolyglyool ether in 4000 parts of water, and 100 parts of a polyarnide fibres are introduced into the dyebath at 25 C. The bath temperature is brought to 100 C. within minutes, the bath is kept at this 4 Example 2 10 parts of 1,8-dihydroxy-4,5-dinitro-anthraquinone and 15 parts of -N-(p-aminophenyl)-pyrrolidone are heated to the boil in parts of dimethyl formamide, until the starting material can no longer be detected by paper chromatography. The reaction mixture is stirred with 750 parts of 10% hydrochloric acid, the precipitated dye-stuff filtered off with suction, washed with water and dried. The dyestuff obtained dyes polyester fibres in intense grey-blue shades. It has the following constitution:

Example 3 8 parts of quinizarine, 2.5 parts of leu-co-quinizarine and 6 parts of boric acid in parts of ethanol are treated while boiling within about 10 hours with .a solution of 8.8 parts of N-(p aminophenyl)-pyrrolidone in 100 parts of ethanol. Boiling is continued fior about 12 hours and the leuco-dyestutf is oxidised, fior example by the addition of 3 parts of sodium perborate in 25 parts of Water. Aiter cooling, the .dye'stuff which has crystallized as blue needles is filtered off with suction, washed with ethanol and Water, stirred, if necessary, with a strongly diluted sodium hydroxide solution in order to remove small amounts of quinizarine, and isolated in known manner. The dyestuff essentially possesses the following constitution:

l H l (FE t and dyes polyester fibres in fast intensely reddish blue shades. Similar dyestuffs are obtained by using, instead of N-(p-anrinophenyl)-pyrro1idone, the m isomer or derivatives substituted in the aromatic nucleus by halogen, alkyl or .alkoxy groups.

Example 4 after conversion into the finely divided form, dyes polyamide and polyester fibres in intense greenish blue shades. A similar dyestuff is obtained by using the p isomer of 4 (m aminophenylamino) n butane sulphonic acid instead of the sultame.

H N (6 OH.

AW m Zia- 3 \ii is filtered 01f with suction, washed with water and dried. The dyestufi dyes polyamide and polyester fibres in intensely greenish blue shades which are even more greenish than the dyeings obtained with the unreduced dyestuff.

'(c) parts of the dyestufi produced according to Example 4(b) are heated in 130 parts of o-dichlorobenzene with 0.1 part of iodine and 3.3 parts of bromine to 50-55 C., until an isolated dyestufi sample contains 1l-l2% of bromine. The o-dichlorobenzene is driven off with steam, the dyestutf filtered otf with suction, washed :with Water and dried. Compared with the dyestuff of Example t-(b), the brominated dyestuif possesses an improved afiinity and dyes polyester fibres in somewhat more reddish shades than the unbrominated dyestufi.

Example 5 (a) 10 parts of 1,5-dinitro-4,8-dihydroxy-anthraquinone and 35 parts of the sult-arne of 4(m'arnin0phenylamino)-n butane+sulphonic acid are heated in 100 parts of glycol to 190 (3., until the starting material can no ionge-r be detected. The reaction mixture is stirred with 500 cc. of 10% hydrochloric acid, filtered off with suction, washed with water and dried. The resulting dyestutf of the formula Ht 3 n0 dyes polyamide and polyester fibres in fast greenish blue shades. A dyestuff with similar properties is obtained by using 1,8adihydroxy 4,S-dinitro anthraquinone instead of 1,5-dinitro-4,8-dihydroxy-an-thraquinone.

Example 6 10 parts of 1,8-dihydroxy-4,5-dinitro-anthraquinone and .21 parts of the sultarne of 4- (m-aminophenyla1ninoy n-tbutane-sulphonic acid are heated to the boil in 100 parts of glycol monoethyl ether, until the starting ma terial can no longer be detected by paper chromatography. The reaction mixture is stirred with 500 parts of 10% hydrochloric acid and, after filtering, washing and drying, a dyestuif of the formula HO (H) ()H I! NC at 2% tag \it is obtained which dyes polyami-de and polyester fibres in intensely greenish blue shades. Similar dyestufl s are obtained by using, instead of the above mentioned sultame, the sultames of N-(Z-arnino 4 chloro phenylamino)-, N-(3-a-mino-4-methylphenylamino)- or N-(4- amino 2,5 dimethoxyphenylamino) n butane sulphonic acid.

Example 7 8 parts of quinizarine, 2.5 parts of leuco-quinizarine and 6 parts of boric acid in 190 parts of boiling ethanol are treated with 14 parts of the sultarne of 4-(p-.aminophenylamino)-n-hutane-sulphonic acid within about 8 hours and boiled, until the condensation is completed. The leuco-dyestuit is oxidised, for example by the addition of a solution of 3 parts of sodium penbonate in 38 parts of Water, the dyestuif is filtered oil with suction after cooling, washed with water and, if necessary, stirred with a strongly diluted sodium hydroxide solution, in order to remove any unreacted quinizarine. The

esulting dyestuii of the formula dyes polyamide and polyester fibres in fast violet shades.

Example 8 7 parts of leuco-l,4,5, 8-tetrahydroxy-anthraquinone, 14 parts of the sultame of 4-(m-aminophenylamino)-n- :butane sulphonic acid and 32 parts of n-butanol are heated to C. for about 10 hours and heated with parts of nitrobenzene and 1.25 parts of piperidine to C. for a further 3 hours. Subsequently, the nitrobenzene is driven oil? with steam and the dyestuif isolated in known manner. The resulting dyestuif of the polyester fibres.

Example 9 12 parts of 4, 8-din-itro-l,S-dihydroxy-authraquinone and 2 2 parts of l-(4-ami-nophenyl)-1,2,4-triazole in 100 parts of glycol monoethyl ether are heated to the boil, until the starting material can no longer be detected chromatographical-ly. The reaction mixture which contains fine blue needles is stirred With 500 parts of 10% hydrochloric acid, the precipitated dyestulf of the formula OgN 0 OH Ht t ua r ll is filtered off with suction, washed and dried. The dyeistuff dyes cellulose acetate, polyamide and polyester fibres in intense fast greenish blue shades. By quaternization of the dyestufi with, for example, dim ethylsulfate, a water-soluble dyestuff is obtained which dyes polyacr-ylonitnile fibres in fast blue shades.

7 Example 10 parts of 4,8-dinitrod,5-dihydroxy-anithraquinone, 5 parts of 4,5-.dinitro-1, 8-dihydroxy anthraquinone, 7.5 parts of lN-(m amino-phenyl)-succinimide and 7.5 parts of N (-p-aminophenyl)-succinirnide in 100 parts of glycol monoethyl ether are heated to the boil, until the reaction is completed. The reaction mixture is subsequently worked up by stirring it into 10% hydrochloric acid. A mixture of dyestuffs of the formulae is thus obtained which dye polyamide and polyester fibres in greenish blue shades. When instead of the N-(aminophenyD-sucoinimide, the corresponding glutaric acid, diglycolic acid or thiodiglycolic acid imides are used, dyestuffs with similar dyeing properties are obtained.

Example 11 10 parts of 4,8-dinitro-l,5-dihydroxyanthraquinone :and parts of N-( p-am'inophenyl)-morpholine in 100 parts of glycol monoethyl ether are heated to the boil, until the starting material can no longer be detected. The reaction mixture is stirred with 500 parts of 10% hydrochloric acid and the resulting dyestufi of the formula/ is isolated. The dyestufi dyes polyamide or polyester fibres in an intensely greenish blue shade. Dyestuifs with similar dyeing properties are obtained by using, instead of N-(-p-aminophenyl)-morpholine, iN-( p-aminophenylythiomor pholine and/or, instead of 4,8-dinitro- 1,5 dihydroxy anthraquin one, 4,5 dinitro 1,8 -rd=ihydroxy-anthraquinone.

Example 12 6.5 parts of quinizarine, 4 parts of l-euco-quinizarine and 6 parts of boric acid in 60 parts of boiling nbutanol are treated within 8 hours with 10 parts of NdmaminophenyD-morpholine dissolved in 40 parts of n-butanol;

The mixture is boiled, until the reaction is completed,

Qthe product which crystallizes as olive-brownish prisms is filtered ofi" with suction after cooling, and the leucodyestufi is oxidized in 80 parts of n-butanol in the pres- ,ence of 1 part of piperidine at 100 C. by means of a en;

The dyest-ufi crystal'l'izing as large red-blue prisms and having the formula I l l N l O NH- dyes polyamide and polyester fibres in blue-red shades. -A dyestuff with similar dyeing properties is obtained by using -N o-aimi-nopheny1)-piperid ine instead of N-(O- aminophenyl -morphol-ine.

Example 13 10 parts of 4,8-dinitro-1,5dihydroxy-anthraquinone and parts of N-(p-aminophenyl)4N-methyl piperazine in 1 00 parts of glycol monoethyl ether are heated to the boil, until the reaction is completed. The product is worked up by stirring with dilute hydrochloric acid, and the dyestuff of the formula OzN is thus obtained which dyes polyarni-de and polyester tfibres in intense blue shades. By quarternizin-g the dyestufi with, for example, dimethyl-sulphate, a water-soluble dyestuff is obtained which dyes polyacrylonitrile fibres in fast blue shades.

I claim: 1. A anthnaquinone dyestufi of the formula a l l wherein R is hydroxyl and Z is a member selected from the group consisting of and o N \e R and R represents a member seleoted thorn the group consisting of nitro, amino, and hydnoxyl.

2. A dyestufi of the tormula Nagy/Q 9 3. A dyestuff of the formula 4. A dyestuff of the formula 1* 1 1 5. A dyestufi of .the iormula HO 0 OH I ll I 0 3 l l l Q O2N O l\IH 6. A dyestufi of the formula I ll HO 0 References C3211 in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Venkataraman: Chemistry of Synthetic Dyes, volume 1 (1952), page 69. 

1. A ANTHRAQUINONE DYESTUFF OF THE FORMULA 